Primary accelerators for sulfur-cured elastomers

ABSTRACT

Simple metal salts are found to be useful as primary accelerators for the sulfur vulcanization of nonpolar, unsaturated hydrocarbon rubbers. Useful metals include those of Group I-A, Group II-A, and transition metals of the periodic table including mixtures thereof. The metals are usually employed in the form of metallo-organic compounds. However, certain inorganic metal salts such as metal halides, carbonates and nitrates are also applicable.

finite taee atet 1191 Fischer [4 1 Sept.9,1975

. 1 Pli.i.. 1ARY ACCELERATORS FOR SULFUR-CUREI) ELASTOMERS [75] Inventor: Wilbur F. Fischer, Cranford, NJ.

[73] Assignee: Exxon Research and Engineering Company, Linden, NJ.

[51] Int. Ch... C08c 11/64; CO8c 11/04; C08d 9/00 [58] Field of Search 260/795, 779, 783, 795, 260/798 [56] References Cited UNITED STATES PATENTS 2,31 1,656 2/1943 Griffith 260/768 2,582,795 1/1952 Prentiss. 260/415 3,322,802 5/1967 Brooks.. 260/429 3,494,900 2/1970 Morita 260/79.5

3,641.21 1 2/1972 Strange 260/889 FOREIGN PATENTS OR APPLICATIONS 1,186,693 4/1970 United Kingdom 260/775 453,477 12/1948 Canada 260/783 1,302,964 7/1962 France 260/795 OTHER PUBLICATIONS Rubber Chem. and Technology, 35, pg 1100 (October-November 1962) Primary ExaminerChristopher A. Henderson, Jr. Attorney, Agent, or FirmE. J. Fanning; W. T. Clarke 1 5 ABSTRACT Simple metal salts are found to be useful as primary accelerators for the sulfur vulcanization of nonpolar, unsaturated hydrocarbon rubbers. Useful metals include those of Group l-A, Group II-A, and transition metals of the periodic table including mixtures thereof. The metals are usually employed in the form of metallo-organic compounds. However, certain inorganic metal salts such as metal halides, carbonates and nitrates are also applicable.

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Wilbur FF/sc/rer INVENTOR Y E N R O T T A PATENTEU 35F 9 sum 2 0 3 I OOm ll OOON Wilbur E Fischer INVENTOR BY ATTORNEY no wmnhqmmmsumh mmDo ATTORNEY sum 3 D5 3 SEP 9 R o m 0% com 9% 00 0mm oon w m I r e I h C 6 F E w com .w W a n d l m 002 a m w m m l d 002 m ooo- PATENTED PRIMARY ACCELERATORS FOR SULFUR-CURE!) ELASTOMERS BACKGROUND OF THE INVENTION It is known that certain metal salts, such as alkali metal organic acid salts, are useful as accelerators in the sulfur cure of some polar polymers such as halogenated elastomers (see, e.g., US. Pat. No. 3,458,461).

It is also known that metal salts such as zinc stea'rate,

zinc oxide, etc., are useful as stabilizers or secondary accelerators in combination with primary accelerators such as thiurum derivatives and dithiocarbamates in the sulfur cure of low unsaturated rubbers.

THE PRESENT INVENTION It has now been unexpectedly discovered that a certain class of simple metal salts may be used as primary accelerators in the sulfur cure of nonpolar, unsaturated hydrocarbon rubbers. This new cure system results in significant economic savings over conventional organosulfur cure systems prcsently in use. For example, compound costs for the instant cure system may be reduced to roughly half that of conventional systems. Further, more economical mixing cycles, i.e., one-step mixes,- may be attained. More importantly, greatly increased cure control (i.e., control of cure over a broad temperature spectrum), use of higher processing temperatures and development of high physical properties (e.g., modulus, rupture tensile, elongation, etc.) at high cure temperatures are possible with the instant vulcanization system.

It should be understood that for purposes of this invention what is meant by nonpolar rubbers are those rubbers having induced dipoles as opposed to rubbers having permanent dipoles such as nitrile rubbers or halogenated rubbers which are classified herein as polar rubbers.

The rubbers for which the novel cure systems of the instant invention are applicable include ethylenepropylene-diene -diene terpolymers (EPDMs). The term EPDM" is used in the sense of its definition as found in ASTM Dl4l8-64. These polymers normally contain about 45 to about 90 wt. ethylene and about 2 to about wt. of a diene monomer, the balance of the polymer being propylene. Preferably, the polymer contains about 50 to about 75 wt. ethylene, e.g., 56 wt. and about 2.6 to about 4 wt. of a diene monomer, e.g., 3.3 wt. The viscosity average molecular weight range is generally 40,000 to 800,000, preferably 80,000 to 450,000, and most preferably 150,000 to 300,000. The diene monomer is preferably a nonconjugated diene. Typical examples of non-conjugated dienes include 5-alkylidene-2-norbornenes such as 5-methylene-2-norbornene, 5-ethylidene-2- norbornene, etc.; 5-alkenyl-2-norbornenes such as 5-vinyl-2-norbornene, 5-( 3 '-butene )-2-norbornene, etc.; 2-alkyl-norbomadienes such as 2-methylnorbornadiene, Z-ethyI-norbornadiene, etc.; acyclic nonconjugated dienes such as 2,4-dimethyl-2,7- octadiene, ll-ethyl-l,l l-tridecadiene, 1,4-hexadiene, etc.; alicyclic non-conjugated dienes such as dicyclopentadiene, 3-methallyl cyclopentene, 1 ,5- cyclooctadiene, etc.; hydroindenes such as 4,7,89- tetrahydroindene, etc.

Other applicable rubbers include butyl rubber, styrene butadiene copolymers (SBRs), polyisoprene, polybutadiene, etc. The term butyl rubber is intended to include copolymers made from a polymerization reaction mixture having therein from to 99.5% by weight of an isoolefin which has about 4 to 7 carbon atoms, e.g., isobutylene, and about 0.5 to 30% by weight of a conjugated multiolefin having from 4 to l4 carbon atoms, e.g., isoprene, piperylene, etc. The resulting copolymer contains to 99.8% by weight of combined isoolefin and 0.2 to 15% of combined multiolefin. Butyl rubber generally has a Staudinger molecular weight of about 20,000 to about 500,000, preferably about 25,000 to about 400,000, especially about 100,000 to about 400,000, and a Wijs iodine number of about 0.5 to 50, preferably 1 to 15.

SBR is well-known to the art. Typically, these polymers contain about 5 to about 40 wt. styrene and have a Wijs iodine number of about 300 to about 500 and a number average molecular weight of about 3,000 to about 600,000, preferably about 100,000 to about 150,000.

Polyisoprene (e.g., natural rubber, gutta-percha, balata and synthetics) and polybutadiene (either cisl,4,trans-1,4 or mixtures) are polymers well-known in the art. They have number average molecular weights in the range of about 3,000 to about 600,000, and preferably 100,000 to about 350,000.

Of course, the metal curatives of the instant invention would also be applicable to blends of nonpolar unsaturated hydrocarbon rubbers, for example, an EPDM-SBR-isoprene blend.

The metal salts which are useful as primary accelerators in the instant invention include salts of the Group I-A, Group II-A, and transition metals of the periodic table of the elements and mixtures thereof. Preferably, the metal to be employed will be one of the following: Cu, K, Mn, Co, Fe, Ce, Zr, Ba, Pb, Zn, Li, Mg, and mixtures thereof.

These metal salts are normally employed in the form of metallo-organic compounds. Although some writers define metallo-organic compounds as including organometallic compounds (i.e., compounds having a direct metal-carbon bond), the more usual definition, and the one used in this invention, includes only compounds in which the metal cation is bonded to the organic moiety (i.e., the anion) through other than a carbon atom, e.g., through an N, P, O, S, etc. This definition is, of course, not meant to exclude compounds which may possess organometallic bonding in addition to the required metallo-organic bonding.

Thus, by metallo-organic compounds is meant to include mono, di, and poly-carboxylic acid salts of the abovementioned metals. Preferably, carboxylic acid salts having a carbon number range of from C to about C (more preferably C to about C will be employed. Illustrative examples of useful carboxylate anions include acetates, stearates, octanoates, neodecanoates, naphthenates, phenolates, phthalates, ricinoleates, acrylates, etc.

Also meant to be included are metal salts of thioacids (e.g., thiolic acids, thionic acids, thiophenol, etc.) and metal alkoxides (e.g., magnesium alcoholates, etc. Preferable carbon number ranges for the thioacids and alkoxides will be the same as for the carboxylic acids. Nonreactive substituents may, of course, also be preserit in the hydrocarbon portion of any of the above -metallo-organic compounds and are meant to be included in the definition thereof.

wherein R is hydrogen or the same or different C -C alkyl radical, a is l or 2 depending on the valence of Y, b is O or 1 depending on the valence of Y, c is an integer from to 3, Y is nitrogen, oxygen, phosphorus or sulfur, and Z is a nonreactive radical selected from the group consisting of (l) C.,C cycloaliphatic or arematic radicals and their lower alkyl derivatives wherein tures to form the accelerating species. Any sins" salt possessing these properties should be useful as an accelerator in the instant invention.

It has been found that there is a relationship between the capacity of a metal salt to accelerate rubber vulcanization and the lattice energy of that salt. Thus, for example, metal oxides which have a lattice energy in the range of from 724 to 4,615 kcal/mole have been found to be ineffective as accelerators for the rubbers of the instant invention. Opposingly, salts such as LiNO ZnCl- ZnOAc and Cu(OAc having lattice energies of 193, 645, 657 and 679 kcal/mole, respectively, are effective accelerators. As a good general rule to employ in selecting useful accelerators, one should select a salt of one of the aforementioned metals which has a lattice energy of less than about 700 kcal/mole. Below this upper limit there is a rather general, but not invariable, relationship between lattice energy and activity order of the metal curatives.

Table 1 below lists lattice energies in kcal/mole of various metal salts:

Lattice energies obtained from Progress in Solid State Chemistry, Vol. I, Chapter 2, The MacMillan Co., N.Y. (1964).

said radicals are attached to the Y atoms at 1,2- positions on the aromatic rings or 1,2- or l,3-positions on the cycloaliphatic rings; and (2) 1 to 4 methylenic radicals wherein each methylenic radical contains 0 to 2 monovalent hydrocarbon radicals of l to 6 carbon atoms.

Suitable nonlimiting examples of compounds falling within the scope of the above formula include: ethanediamine (EDA), N,N,N', N'-tetramethyl ethanediamine (TMED), N,N,N', N", N"-pentamethyl diethylene-triamine (PMDT), beta-(dimethylamino) ethyl methyl ether, ortho-dimethylamino anisole, beta- (dimethylamino)ethyl methyl sulfide, ldimethylamino-Z-dimethylphosphine, cis-N,N,N', N'- tetramethyl-l,2-cyclopentane diamine, diethylene glycol dimethyl ether (diglyme), etc.

The major considerations in selecting the anion portion of the salt are ease of dispersion of the salt at processing temperatures of 100250F. and effectiveness in curing the rubber at higher temperatures of 300475F. Some factors involved are solubility of the salt in the rubber compound, particle size, and ability to complex with the sulfur at vulcanization tempera- Representative examples of preferred anions to be used in combination with cations of the metals listed above to form the metal accelerators of the instant invention include but are not limited to the acetate, octoate, neodecanoate, naphthenate, carbonate, chloride,

etc.

While the above discussion indicates applicable anions, it must be noted that the most important consideration in determining the metal accelerator to be employed in a particular process is the type and amount of metal ion. The anion portion of the salt is important only insofar as it allows the metal to be efficiently incorporated in the rubber and does not unduly restrict its activity so as to allow it to function as a primary accelerator. For example, at a constant lead content three different lead organo compounds of Table ll, being easily dispersible in the rubber (an EPDM having 52 wt. ethylene, 45 wt. propylene and 3 wt. diene monomer) cured to give similar results within each group of measurements. Results indicate the anion portion of the curative is important only to conferring solubility in the rubber and thereafter has little effect on vulcanization events.

TABLE II EFFECT OF ORGANO PORTION OF LEAD CURATlVE Constant Lead Content 1 phr NOTE: Initial tensile and modulus maxima coincided in all cases at H) at 375F.

TABLE Ill blacks are useful in the present invention. The more chemically active, highly oxygenated channel and furnaee blacks are preferred sinceit has been discovered that these types of blacks may themselves effectively cocure rubbers with element sulfur without additional accelerators when high temperature curing techniques (e.g., temperatures in the range of about 400 to about 500F.) are employed. For example, the nonaccelerated sulfur cure of EPDM produces a 200% modulus of only 350 psi for the least active thermal black (MT) at 490F. but 900 psi and 1 100 psi for the more ACCELERATION BY SIMPLE ZINC COMPOUNDS Maximum Stress Levels Zinc Curativc* Cure Activity 5' Cmpd Zinc initiation Optimum 2007:

Type phr phr F. F, Tensile Modulus Elong.

Chloride 2 ll) 3 l5 400 I630 780 450 Acetate 2 0.7 1H8 410 I700 820 430 Stearatc (L8 0.7 326 400 1720 670 520 Chromate 2 0.7 345 470 1610 700 500 Oxide 390 390 I500 550 530 5 Zinc oxide; 1 slearic acid; 2 A sulfur, common to all compounds,

Although the amount of metal to be employed as an accelerator in the vulcanization of the types of rubbers hereinbefore described is dependent to some extent on the activity of the metal used, generally from about 0.25 to about 10 parts, and preferably 1 to 4 parts, of metal salt are employed per hundred parts of rubber.

Rubbers are usually compounded with a variety of other ingredients using a two-step mix with the sulfur and/or accelerators added in the second step. This, in fact, was the compounding procedure followed in preparing the materials shown in Tables ll, ill, V and VI herein. A representative composition (all components shown are in parts per hundred rubber phr) would be:

1 Masterbatching Mix 2 m Acceleration Mix Rubber 1 Masterbatch i50450 Zinc Oxide Sulfur 2 Stearic Acid 2 Accelerators 0.25- Carbon Black 50-200 Oil Plasticizcr l0l0() Filler masterbatching is usually accomplished in an internal mixer (e.g., a Banbury mixer) that shears the rubber and effectively disperses the dry ingredients and oil in 2--l5 mixes to dump temperatures of 250350F. Vulcanizing agents can be added to the masterbatch either on the mill or in a second Banbury mix in about 2 to about 5 minutes to 250F. mix temperatures. Thereafter, the rubber is formed and vulcanized into its permanent shape in about to about 1 minute, at 300450F. temperatures, respectively, using various methods (e.g., compression or injection molding, extrusion and continuous vulcanization, autoclave curing, etc.) it should be noted that while such a two-step mix was employed herein in order to obtain uniformity of results by using the same masterbatch, the present invention allows one-step mixes to be readily employed.

Any of the well-known oil plasticizers and carbon active EPC and HAF carbon blacks, respectively. Maximum rupture tensile which develops somewhat earlier (about 460F. measured 1200 psi/MT, 2000 psi/EPC and 1700 for the HAF carbon black. Thus, when used in combination with the metal accelerators of the instant invention even more effective cures may be attained, particularly at higher temperatures.

Examples of preferred blacks include the low and high structure furnace blacks, channel black, etc., which now readily cure at 390F. using only sulfur and zinc acetate as the cure system.

It has also been discovered that the metal salts of the instant invention may be classified in order of metal activity according to cure initiation which covers a temperature range from about 285 to about 390F. Table IV below indicates this activity which was calculated using an EPDM having the following physical properties: 52 wt. ethylene, 45 wt. propylene, 3 wt. diene, a viscosity average molecular weight of 150,000 and a Mooney viscosity ML of 60 at 260F. Although the activity order was calculated using an EPDM, the same order of activity, with minor variations in temperature, would be expected for any of the rubbers useful in the instant invention.

This activity order was determined using the gradient temperature zero modulus method. For an excellent discussion of this method, see the article by W. F. Fi-

7 scher appearing in Rubber A ge (Aug. 1970), pp. 54-69.

By using the above information concerning activity order, it is possible for one skilled in the art to readily determine the most desirable accelerator or mixtures of accelerators to employ under any time-temperature condition of processing or vulcanization. For example, copper neodecanoate which activates cure in at 286F. would be used to quickly cure soft low-hardness compounds where mechanical heat buildup is not a problem. To prevent undesirable prevulcanization during processing of tough high-hardness compounds, cerium neodecanoate might be selected since vulcanization does not begin before 5 at 319F. (equivalent to 25' at 286F.). This orderly cataloging of metal accel- 7 erator activity is very useful since the time-temperature relation of chemical reactions follows a generally accepted rule which indicates that for each F. rise in temperature the rate increases by a fixed factor or temperature coefficient of 1.5. (See, The Vanderbilt Rubber Handbook, p. 622, Bryant Press, Inc., New York (1968).) Optimum vulcanization time in this case is reduced by one-third, e.g., optimum cures occur at 9/3 10F. or 6/320F. Thus the problem of prevulcanization and location of optimum vulcanization conditions is substantially obviated.

Table V, below, is representative of the unusual ability of metal curatives of the instant invention to control the location, level and duration (stability) of vulcanization events. The anion employed is a neodecanoate in each case. However, as discussed previously, the metal type and not the anion is the most important consideration and any of the previously mentioned applicable anions would give similar results.

It can be seen from the information in Table V that one may, if desired, select a mixture of metal curatives so as to effect both early cure initiation and very broad duration of cure. Thus, for example, a combination of copper and lithium salts would result in cure initiation at about 286F. for a 5-minute cure and attain crosslink stability over the range of from about 340-5 F.

Use of the accelerators of the instant invention also enables production of high strength vulcanizates over the temperature range of from about 300 to about ()F. The prior art conventional organo-sulfur curatives are normally used in a range of 300-400F., and at temperatures much over 400F. efiective control of vulcanization events is questionable with the likelihood of production of relatively unstable materials. By contrast, the instant invention enables production of vulcanizates having high physical properties 'over the 400-5 50F. temperature range. This may be illustrated by reference to FIGS. 1 and 2, which represent plots of 300% modulus vs. S-minute cure at 300550F. for both the metal curatives of the instant invention and the prior art tetramethyl thiuram disulfide (TMTDS) cure. The anion employed in all cases for the metal curatives of the instant invention was a neodecanoate and the rubber employed was an EPDM having the following physical properties: 52 wt. ethylene, 45 wt. propylene, 3 wt. diene, a viscosity average molecular weight of 150,000 and a gum Mooney viscosity ML of at 260F. As in Table V, the compound contained 140 parts of carbon black and 60 parts of oil.

Prior art curatives such as TMTDS initiate cure over the temperature range of about 285-340F., presumably by the formation of predominantly long polysulfidie cross-links. However, it can be seen from the TABLE V USE OF MEI'AL SALTS OF NEO ACIDS AS VULCANIZATION ACCELERATORS FOR EPDM(3) 5' Cure Minimum Initiation Maximum Physicals Elongation Crosslink Stability Metal phr(0) F. 3007: Mod.-Rating( I Tensile at Mod.Max. Range, F.(2) Spread Rating( I Copper-2 286 820 4 I560 610 340-440 I00 6 Potassium-2 292 830 4 I580 610 360-470 I I0 6 Manganese-2 305 760 5 I400 540 385-550+ I 3 (Double Peak) Cobalt-4 312 760 5 I520 680 355-430 8 Iron-2 315 900 3 I500 530 370-440 70 8 Cerium-2 3 I 9 950 3 I400 420 390-530 I 40 4 Zirconium-4 322 860 4 I330 530 380-550 I I Barium-4 323 I 170 l 1520 420 395-545 I50 4 Lead-4 330 780 5 I600 610 360-5 10 I 50 5 Zinc-4 332 950 3 I550 5 I0 375-540 I65 2 Lithium-l 345 1 I20 2 I I20 300 400-550 150 4 Magnesium-I 345 I 100 2 I380 420 410- 550 I40 3 Calcium-2 388 960 3 I370 410 455-550 95 7 TMTDS-S (Control) 285 900 3 I620 530 345-440 8 Parts per I00 phr as metal salt C, new acid.

Rating l (best); highest modulus or stability.

Extreme temperature within which 80% of maximum 300% modulus is retained.

(3) EPDM same as employed in Table IV.

FORMULATION EPDM I00 Stearic Acid I Zinc Oxide 5 SRF Black I40 Flexon 791 Oil 60 Sulfur 2 Metal Salt l-4 (as indicated) Exception:

TMTDS 2.3 Sulfur 2.5

above-mentioned figures that beyond the modulus peak at approximately 400F. for TMTDS, asubstantial for high temperature vulcanization over the conventional organo-sulfur curatives.

' TABLE VI CONVERSION OF SULFUR TO CROSS-LINKS AT 500F.. EPDM 300% '7! of 300'?! '7: of Metul-NDC Modulus Mux. XLD" Metul-NDC Modulus Mux. Xl.D"

Barium l l 94 Mungunese 730 hi Lithium i090 9| Loud 630 53 Magnesium: 1060 89 Copper 520 43 Culcium 970 ill lron 450 37 Cerium 900 75 Cobalt 380 32 Zinc 820 68 TMTDS 500 42 Zirconium 800 67 Sulfur only 900 75 "'Neodecunoule.

*By setting the muximum modulus for any curative anywhere in the cure history at 100% in this ease hurium. i200 psi at 5/430F., o relntive measure of cross-linking efficiency at 500F. was derived by: '71 Eff. (500"F.) M; (500F.)

50% decrease in modulus occurs over the temperature range of about 450500F. By contrast, it can be seen from the same figures. that modulus levels for many of the metal curatives of the instant invention (e.g., Ba, Ce) are quite high and yield a desirably flat response over the same temperature region. This has a very desirable influence on rupture tensile as exemplified in FIG. 3. Thus, the metal curatives provide improved control of cure state which strongly influences the quality of rubber parts.

These figures and the information in Table V above also reflect significant differences in sulfur cross-link density and type. Modulus measurements are directly proportional to the number (density) of cross-links formed during the vulcanization process. High moduli indicate more efficient use of available sulfur by the curative and rubber. The type of sulfur cross-link is also important since long polysulfidic cross-links are less stable than the more desirable mono and disulfidic or carbon-carbon cross-links. The flat portions of the modulus curves (of, e.g., Li, Ba) over a 425550F. curing range in FIGS. 1 and 2 reflect unusually high efficiency and stability that can only result from a high proportion of stable cross-link types.

Table V shows that the metal curatives were evaluated at 2.0 parts sulfur and the conventional thiuram accelerators at 2.5 parts sulfur. Despite this, the higher moduli and shorter rupture elongation of the barium, cerium and lithium salts indicate a tighter, denser sulfur cross-linked network has been attained than with con- Further, by operation in high temperature regions, quite short cure times may be effected. For example, while cure times in the prior art are often in the region of one-half hour, high temperature cures using the present metal curatives result in effective cures in from 5 to as little as 0.5 minutes.

The following additional example is meant to further illustrate, but in no way limit, the instant invention:

EXAMPLE 1:1 complexes of various metal salts of the instant invention were prepared with the materials listed in Table VII below. These complexes were then employed as primary accelerators for the sulfur vulcanization of an EPDM having 52 wt. ethylene, 3 wt. diene, a viscosity average molecular weight of 150,000 and a Mooney viscosity ML of at 260F. The formulation in each case was parts EPDM, 5 parts zinc oxide, 1 part stearic acid, parts semi-reinforcing furnace black, 60 parts naphthenic oil, 2 parts sulfur, and 2 parts accelerator. The materials were compounded in a Banbury, an internal rotor type mixer. All powdered ingredients (except sulfur and metal curative) and oil were added to the mixer with the rubber added last. The homogenized mix was dumped at 300F. after 8 minutes. Curatives and sulfur were then added on a mill at 200F. Strips were then cured 10 minutes at 300550F. gradient temperatures. The results are shown in Table VI] below.

"PMDT Pentamethyl diethylene triamine.

TMEDA Tetramethyl ethylene diamine. DiGlyme Diethylene glycol dimethyl ether. EDA EThylenc diamine.

ventional thiuram (TMTDS) cure.

Further evidence for this observation is tabulated in Table VI below, where it can be seen that the instant metal curatives offer improved efficiency and stability From this table it can be seen that simple zinc diacetate along produces a high cure state similar to the zinc acetate complexes. This further confirms that the zinc cation is dominating cure behavior.

salt the anion of which is selected from the group consisting of acetate, chloride, nitrate, thiocyanate, octoate, naphthenate, or neodecanoate, and the metal being selected from the metals of Group l-A, Group II-A, or transition metals wherein said salt has a lattice energy of less than about 700 kcal/- mole; wherein the metal salt is complexed with diethylene glycol dimethyl ether (diglyme); and

b. heating the product of step (a) to a temperature in the range of about 300 to about 550F. in order to effect curc. 

1. A PROCESS FOR THE SULFUR VULCANIZATION OF A NONPOLAR UNSATURATED HYDROCARBON RUBBER WHICH CONSISTS ESSENTIALLY OF: A. ADDING TO 100 PARTS OF SAID RUBBER A VULCANIZABLE AMOUNT OF SULFUR AND FROM 0.25 TO 10 PARTS OF A PRIMARY ACCELERATOR CONSISTING ESSENTIALLY OF A METAL SALT THE ANION OF WHICH IS SELECTED FROM THE GROUP CONSISTING OF ACETATE CHLORIDE NITRATE THIOCYANATE OCTOATE, NAPHTHENATE OR NEODECANOATE, AND THE METAL BEING SELECTED FROM THE METALS OF GROUPS I-A, GROUP II-A OR TRANSITION METALS WHEREIN SAID SALT HAS A LATTICE ENERGY OF LESS THAN ABOUT 700 KCAL/MOLE WHEREIN THE METAL SALT IS COMPLEXED WITH DIETHYLENE GLYCOL DIMETHYL ETHER(DIGLYME), AND B. HEATING THE PRODUCT OF STEP (A) TO A TEMPERATURE IN THE RANGE OF ABOUT 300* TO ABOUT 550*F IN ORDER TO EFFECT CURE. 